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41.
Moriarty RM Rani N Enache LA Rao MS Batra H Guo L Penmasta RA Staszewski JP Tuladhar SM Prakash O Crich D Hirtopeanu A Gilardi R 《The Journal of organic chemistry》2004,69(6):1890-1902
A general and novel solution to the synthesis of biologically important stable analogues of prostacyclin PGI(2), namely benzindene prostacyclins, has been achieved via the stereoselective intramolecular Pauson-Khand cyclization (PKC). This work illustrates for the first time the synthetic utility and reliability of the asymmetric PKC route for synthesis and subsequent manufacture of a complex drug substance on a multikilogram scale. The synthetic route surmounts issues of individual step stereoselectivity and scalability. The key step in the synthesis involves efficient stereoselection effected in the PKC of a benzoenyne under the agency of the benzylic OTBDMS group, which serves as a temporary stereodirecting group that is conveniently removed via benzylic hydrogenolysis concomitantly with the catalytic hydrogenation of the enone PKC product. Thus the benzylic chiral center dictates the subsequent stereochemistry of the stereogenic centers at three carbon atoms (C(3a), C(9a), and C(1)). 相似文献
42.
Masson JF Battaglia TM Davidson MJ Kim YC Prakash AM Beaudoin S Booksh KS 《Talanta》2005,67(5):918-925
The elimination or minimization of non-specific protein adsorption from serum is critical for the use of surface plasmon resonance (SPR) sensors for in vitro and in vivo analysis of complex biological solutions. The ultimate goals in this application are to minimize non-specific adsorption of protein and to maximize analyte signal. A reduction of the non-specific protein adsorption from serum of up to 73% compared to carboxymethylated-dextran 500 kDa (CM-dextran) was achieved following a survey of eight biocompatible polymers and 10 molecular weights of CM-dextran. These coatings minimize non-specific adsorption on the sensor while also serving as immobilization matrices for antibody fixation to the probes. Polymers including polysaccharides: CM-dextrans, CM-hyaluronic acid, hyaluronic acid, and alginic acid were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisuldfide–polyethyleneglycol–N-hydroxysuccinimide (OPSS–PEG–NHS), and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA) were also used. The non-specific protein adsorption reduction was measured over a 14 day period at 0 °C for each polymer. Calibration curves using some of these polymers were constructed to show the performance and low detection limit possibilities of these new antibody supports. For many of the polymers, this is the first demonstration of employment as an antibody support for an optical or surface active sensor. CM-dextran is the polymer offering the largest signal for the antigen detection. However, the biocompatible polymers demonstrate a greater stability to non-specific binding in serum. These biocompatible polymers offer different alternatives for CM-dextran. 相似文献
43.
A solid state copper(II) ion sensor is reported based on the application of electropolymerized undoped (neutral) polycarbazole
(PCz) and polyindole (PIn) modified electrodes. The new sensor shows high selectivity to Cu2+ ions with a detection limit of 10–5 M. PCz and PIn are formed respectively by the anodic oxidation of 50 mM carbazole and 5 mM indole monomers in dichloromethane
containing 0.1 M tetrabutylammonium perchlorate on a platinum electrode using a single compartment cell. Potentiostatic polymerization
of both the monomers are carried out at 1.3 V and 1.0 V vs. Ag/AgCl, respectively. Perchlorate ions were electrochemically
removed from the polymer films by applying – 0.2 V vs. Ag/AgCl. Polymer-coated electrodes are incubated in 1 M KCl solution
for 8 h followed by incubation in distilled water for 2 h before using as a metal ion sensor. The undoped PCz and PIn electrodes
were found to be highly selective and sensitive for Cu2+ ions with little selectivity for Pb2+ and negligible response towards Ag+, Hg2+, Cu+, Ni2+, Co2+, Fe2+, Fe3+ or Zn2+. Potentiometric responses for Cu2+ ions are recorded for both the sensor electrodes together with a double-junction Ag/AgCl reference electrode. Calibration
curves for Cu2+ are reported for both ion sensors. The polymer-modified electrodes were found to be stable for several weeks.
Electronic Publication 相似文献
44.
45.
G. A. Olah G. K. Surya Prakash P. Donald Katherine B. Loker Koop Lammertsma 《Research on Chemical Intermediates》1989,12(2):141-159
In this short review we have shown the importance of protosolvation of onium ions (containing non-bonded pairs of electrons)
in superacid catalyzed reactions. Such activation can result in unusual reactions such as aromatic alkylation with Meerwein’s
salts, aliphatic nitration with nitronium ion, alkylation of saturated hydrocarbons, greatly enhanced activity of acyl cations,
etc. Possibly such phenomena may be operative in hydroxylation reactions using protonated hydrogen peroxide in strong acid
solutions. Even the reactivity of halonium ions could be enhanced by protosolvation. Consequently, electrophilic protosolvation
may play a significant role in strogg acid catalyzed reactions. 相似文献
46.
Scientific evidence in the prevention and treatment of various disorders is accumulating regarding probiotics. The health
benefits supported by adequate clinical data include increased resistance to infectious disease, decreased duration of diarrhea,
management of inflammatory bowel disease, reduction of serum cholesterol, prevention of allergy, modulation of cytokine gene
expression, and suppression of carcinogen production. Recent ventures in metabolic engineering and heterologous protein expression
have enhanced the enzymatic and immunomodulatory effects of probiotics and, with time, may allow more active intervention
among critical care patients. In addition, a number of approaches are currently being explored, including the physical and
chemical protection of cells, to increase probiotic viability and its health benefits. Traditional immobilization of probiotics
in gel matrices, most notably calcium alginate and κ-carrageenan, has frequently been employed, with noted improvements in
viability during freezing and storage. Conflicting reports exist, however, on the protection offered by immobilization from
harsh physiologic environments. An alternative approach, microencapsulation in “artificial cells,” builds on immobilization
technologies by combining enhanced mechanical stability of the capsule membrane with improved mass transport, increased cell
loading, and greater control of parameters. This review summarizes the current clinical status of probiotics, examines the
promises and challenges of current immobilization technologies, and presents the concept of artificial cells for effective
delivery of therapeutic bacterial cells. 相似文献
47.
Daniel L. Obrzut Prakash M. Adekkanattu Jyothi Thundimadathil Jing Liu Delphine R. Dubois James A. Guin 《Reaction Kinetics and Catalysis Letters》2003,80(1):113-121
SAPO-34 silicoaluminophosphate molecular sieve produces large amounts of methane at elevated temperatures in the methanol
to olefins (MTO) process. This significantly reduces the lower olefins selectivity a key factor in determining the commercial
viability of this catalyst. Impregnation of the SAPO-34 molecular sieve with metal ions such as K, Cs, Pt, Ag and Ce was found
to reduce the amount of methane significantly at higher temperatures thereby increasing the lower olefins selectivity. This
observed effect is less apparent at lower temperatures where the amount of methane formed is generally low.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
48.
Determination of organophosphate pesticides at a carbon nanotube/organophosphorus hydrolase electrochemical biosensor 总被引:7,自引:0,他引:7
Randhir Prakash Deo Joseph Wang Ines Block Ashok Mulchandani Kanchan A. Joshi Marek Trojanowicz Fritz Scholz Wilfred Chen Yuehe Lin 《Analytica chimica acta》2005,530(2):185-189
An amperometric biosensor for oganophosphorus (OP) pesticides based on a carbon nanotube (CNT)-modified transducer and an organophosphorus hydrolase (OPH) biocatalyst is described. A bilayer approach with the OPH layer atop of the CNT film was used for preparing the CNT/OPH biosensor. The CNT layer leads to a greatly improved anodic detection of the enzymatically generated p-nitrophenol product, including higher sensitivity and stability. The sensor performance was optimized with respect to the surface modification and operating conditions. Under the optimal conditions the biosensor was used to measure as low as 0.15 μM paraoxon and 0.8 μM methyl parathion with sensitivities of 25 and 6 nA/μM, respectively. 相似文献
49.
The progress of high temperature processes is generally described in terms of variation of the degree of conversion () with time (t). The present paper outlines a procedure for making use of-t plots for comparative assessment of productivity and energy requirements for a test system with respect to a reference, on the basis of some simplifying assumptions. It is assumed that the throughput is inversely proportional to reaction time as in the case of batch reactors and plug flow reactors. It is also assumed that the energy requirement is a simple function of process temperature. The principles outlined is illustrated with reference to some laboratory data for reduction of iron oxide by coal.The authors wish to thank Prof. P. R. Rao, Director National Metallurgical Laboratory, Jamshedpur, India, for providing facilities for experimental work and for according permission to publish this work. 相似文献
50.